Showing papers on "Mass action law published in 1968"
TL;DR: In this article, the thermal energy band gap, the intrinsic carrier concentration, the electron and hole mobilities and the mobility ratio of intrinsic PtSb2, were derived from Hall coefficient and resistivity measurements in the mixed conduction range (77-300°K).
14 citations
Journal Article•
TL;DR: In this article, the generalized rate equation of the absolute rate theory was compared with the mass action law as its special case in the case of an appreciable interaction, especially when it varies, e.g. with change of concen- trations in question, the rate of step could only be reasonably deduced from the statistical mechanics of the whole mass of interacting species which is usually macroscopic and in thermal equilibrium.
Abstract: Summary The mass action law successfully applied to homogeneous elementary reactions (or steps for short) was shown applicable to heterogeneous steps only in unexpectedly limited cases on account of the quantum-mechanically inferable interaction among adsorbed species. In case of an appreciable interaction, especially when it varies, e. g. with change of concen trations in question, the rate of step could only be reasonably dedt:ced from the statistical mechanics of the whole mass of interacting species which IS usually macroscopic and in thermal equilibrium.7,S) The rate equation thus deduced is called the generalized rate equation, which includes the rate equation of the absolute rate theory,I.2) applicable along with the mass action law, as its special case. The generalized rate equation was illustrated and the critical state of a step was located for contrasting the generalized rate equation with the absolute rate theory,l,2) The rates of the Langmuir-Hinshelwood and Rideal mechanisms were derived as functions of concen trations of reactants in gas phase by the mass action law, on the one hand, and by the generalized rate equation ignoring the interaction among adsorbates, on the other hand. The functional forms obtained in the respective cases were identical as otherwise generally demonstrated and their comparison revealed the statistical mechanical contents of kinetic constants involved in the former derivation, directing toward the incorporation of interaction. The incorporation of interaction was exemplified systematically as follows with the catalytic mechanism of hydrogen electrode reaction, where the recombination of hydrogen adatoms determined the rate.